U.S. patent application number 17/416118 was filed with the patent office on 2022-03-10 for polymer composition, article comprising said composition and use of said article.
The applicant listed for this patent is SABIC GLOBAL TECHNOLOGIES B.V.. Invention is credited to Christelle Marie Hee GREIN, Jing GUO, Chaodong JIANG, Chunfa LI, Sarah VAN MIERLOO, Ji ZHOU.
Application Number | 20220073717 17/416118 |
Document ID | / |
Family ID | |
Filed Date | 2022-03-10 |
United States Patent
Application |
20220073717 |
Kind Code |
A1 |
GUO; Jing ; et al. |
March 10, 2022 |
POLYMER COMPOSITION, ARTICLE COMPRISING SAID COMPOSITION AND USE OF
SAID ARTICLE
Abstract
The present invention relates to a polymer composition,
comprising a polypropylene and a stabilizing additive mixture,
wherein said stabilizing additive mixture comprises: i) a thioether
compound according to Formula I, ii) a Hindered Amine Light
Stabilizer (HALS) comprising a substituted amine group; and iii) an
inorganic acid scavenger. The present invention further relates to
an article comprising said polymer composition, and the use of said
polymer composition for the housing for antennas for wireless
communication.
Inventors: |
GUO; Jing; (GELEEN, NL)
; VAN MIERLOO; Sarah; (GELEEN, NL) ; LI;
Chunfa; (GELEEN, NL) ; ZHOU; Ji; (GELEEN,
NL) ; JIANG; Chaodong; (GELEEN, NL) ; GREIN;
Christelle Marie Hee; (GELEEN, NL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SABIC GLOBAL TECHNOLOGIES B.V. |
Bergen op Zoom |
|
NL |
|
|
Appl. No.: |
17/416118 |
Filed: |
December 19, 2019 |
PCT Filed: |
December 19, 2019 |
PCT NO: |
PCT/EP2019/086410 |
371 Date: |
June 18, 2021 |
International
Class: |
C08L 23/12 20060101
C08L023/12; H01Q 1/42 20060101 H01Q001/42 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 19, 2018 |
CN |
201811557188.4 |
Claims
1. A polymer composition, comprising a polypropylene and a
stabilizing additive mixture, wherein said stabilizing additive
mixture comprises: i) a thioether compound according to Formula I:
##STR00005## wherein Q.sup.1 and Q.sup.2 are each independently an
alkyl spacer having between 1 and 6 carbon atoms; R.sup.1 and
R.sup.2 each independently being an alkyl group having between 14
and 26 carbon atoms; O being oxygen and S being sulphur; ii) a
Hindered Amine Light Stabilizer comprising a substituted amine
group; and iii) an inorganic acid scavenger.
2. The polymer composition according to claim 1, wherein the
polypropylene is a heterophasic propylene copolymer consisting of a
propylene-based matrix and a dispersed ethylene-.alpha.-olefin
copolymer.
3. The polymer composition according to claim 2, wherein the
heterophasic copolymer comprises between 70 and 90 wt. % of said
matrix and between 10 and 30 wt. % of said dispersed-phase
ethylene-.alpha.-olefin copolymer.
4. The polymer composition according to claim 1, wherein Q.sup.1
and Q.sup.2 are each --CH.sub.2CH.sub.2--; R.sup.1 and R.sup.2 each
--C.sub.18H.sub.37.
5. The polymer composition according to claim 1, wherein in the
substituted amine group in the HALS is a --N(R)-- group; wherein R
is a hydrocarbyl group.
6. The polymer composition according to claim 5, wherein the
Hindered Amine Light Stabilizer has a structure represented by
Formula IIa or IIb ##STR00006## wherein: R.sup.3, R.sup.4, R.sup.5
and R.sup.6 are each independently an alkyl group having 1-3 carbon
atoms; R.sup.7 is --O--C(.dbd.O)--R.sup.9; L is
--O--C(.dbd.O)--R.sup.10--C(.dbd.O)O--; R is either directly linked
to the nitrogen atom (--R.sup.8) or connected via an oxygen atom
(--OR.sup.8); R.sup.8 is an optionally substituted, optionally
branched alkyl group having between 2 and 10 carbon atoms; R.sup.9
is an alkyl group having between 4 and 14 carbon atoms; and
R.sup.10 is an alkyl group having between 4 and 14 carbon
atoms.
7. The polymer composition according to claim 1, wherein the
inorganic acid scavenger is a hydrotalcite.
8. The polymer composition according to claim 1, wherein the
composition further comprises a sterically hindered phenolic
antioxidant.
9. The polymer composition according to claim 1, wherein the
composition further comprises a phosphite antioxidant.
10. The polymer composition according to claim 1, wherein the
thioether compound is present in an amount of between 0.10 and 1.0
wt. %, of the total polymer composition.
11. The polymer composition according to claim 1, wherein the
Hindered Amine Light Stabilizer is present in an amount of between
0.05 and 0.75 wt. %, of the total polymer composition.
12. The polymer composition according to claim 1, wherein the
inorganic acid scavenger compound is present in an amount of
between 0.05 and 0.75 wt. %, of the total polymer composition.
13. The polymer composition according to claim 1, wherein the
composition further comprises short glass fibre.
14. Article comprising the polymer composition of claim 1.
15. The article according to claim 14, wherein the article is a
housing for antennas for wireless communication.
16. The polymer composition according to claim 6, wherein R.sup.3,
R.sup.4, R.sup.5 and R.sup.6 are each methyl; and R.sup.8 is a
branched alcohol group.
17. The polymer composition according to claim 1, wherein the
composition further comprises a polyphenolic antioxidant.
18. The polymer composition according to claim 17, wherein the
polyphenolic antioxidant is pentaerythritol
tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate).
19. The polymer composition according to claim 13, wherein the
short glass fibre is present in an amount of 5 and 50 wt. % of the
total polymer composition.
20. The polymer composition according to claim 13, wherein the
short glass fibre is present in an amount of 25 and 35 wt. %, of
the total polymer composition.
Description
TECHNICAL FIELD
[0001] The present invention relates to a polymer composition
comprising a polypropylene and a stabilizing additive mixture. The
present invention further relates to an article comprising such a
polymer composition, and the use of such a polymer composition for
the housing for antennas for wireless communication.
BACKGROUND
[0002] Plastic housings for telecom communication antennas are
known. There are several severe requirements to which the polymer
compositions have to comply in order to be suitable for use in
antenna housing, such as a high temperature resistance, good
ultraviolet absorption resistance, good ageing resistance, good
shock resistance, good insulating capacity, good crazing
resistance, good corrosion resistance, and high mechanical and
dimensional strength. These antenna housings may be located in a
severe environment and should resist deformation and
deterioration.
SUMMARY
[0003] It is an object of the present invention to provide a
polymer composition with improved resistance to heat and
weathering.
[0004] It is a further object of the present invention to provide
an article with improved resistance to heat and weathering.
[0005] Corresponding embodiments are also applicable for the
article and the use of an article according to the present
invention.
[0006] One or more of these objects are achieved by a polymer
composition, comprising a polypropylene and a stabilizing additive
mixture, wherein said stabilizing additive mixture comprises:
[0007] i) a thioether compound according to Formula I:
##STR00001##
[0008] wherein Q.sup.1 and Q.sup.2 are each independently an alkyl
spacer having between 1 and 6 carbon atoms, preferably being
--CH.sub.2CH.sub.2--; R.sup.1 and R.sup.2 each independently being
an alkyl group having between 14 and 26 carbon atoms, preferably
between 16 and 20 carbon atoms, such as --C.sub.18H.sub.37; O being
oxygen and S being sulphur; [0009] ii) a Hindered Amine Light
Stabilizer (HALS) comprising a substituted amine group; and [0010]
iii) an inorganic acid scavenger.
[0011] A "substituted amine group" as used in the present
description means a group comprising a nitrogen atom that is
substituted with other atoms than hydrogen. In other words, no
--N(--H)-- group. In an embodiment, the substituted amine group is
an --N(--OR)-- group or an --N(--R)-- group wherein R is not a
hydrogen.
[0012] It was surprisingly found that this above composition
provides polymer products with improved heat resistance as well as
weatherability and good dimensional and mechanical properties.
[0013] The invention further relates to an article comprising such
a polymer composition, and to the use of such a polymer composition
for the housing for antennas for wireless communication.
DESCRIPTION OF EMBODIMENTS
[0014] In an embodiment of the present invention, the polypropylene
is a heterophasic propylene copolymer consisting of a
propylene-based matrix and a dispersed ethylene-a-olefin copolymer.
In a specific embodiment, the heterophasic propylene copolymer has
a melt flow rate of between 0.1 and 10.0 g/10 min as determined in
accordance with ISO 1133:1-2011 (230.degree. C., 2.16 kg). In a
specific embodiment the heterophasic copolymer comprises between 70
and 90 wt % of said matrix and between 10 and 30 wt. % of said
dispersed phase.
[0015] In an embodiment, Q.sup.1 and Q.sup.2 are each
--CH.sub.2CH.sub.2--; R.sup.1 and R.sup.2 each --C.sub.18H.sub.37.
This is a dialkyl ester of thiodipropionic acid, with CAS no:
693-36-7, and it is commercially available for instance under the
name Irganox PS 802 FL from BASF.
[0016] In an embodiment, the substituted amine group in the HALS is
a --N(R)-- group; wherein R is a hydrocarbyl group. In a specific
embodiment, the HALS is according to Formula IIa or IIb
##STR00002## [0017] wherein: [0018] R.sup.3, R.sup.4, R.sup.5 and
R.sup.6 are each independently an alkyl ground having 1-3 carbon
atoms; [0019] R.sup.7 is --O--C(.dbd.O)--R.sup.9; [0020] L is
--O--C(.dbd.O)--R.sup.10--C(.dbd.O)O-- [0021] R is either directly
linked to the nitrogen atom (--R.sup.8) or connected via an oxygen
atom (--OR.sup.8); [0022] R.sup.8 is an optionally substituted,
optionally branched alkyl group having between 2 and 10 carbon
atoms, such as between 3 and 5 carbon atoms; [0023] R.sup.9 is an
alkyl group having between 4 and 14 carbon atoms; [0024] R.sup.10
is an alkyl group having between 4 and 14 carbon atoms.
[0025] In a further embodiment, in Formula IIa or IIb,
R.sup.3.dbd.R.sup.4.dbd.R.sup.5.dbd.R.sup.6.dbd. methyl. In a
further embodiment, in in Formula IIa or IIb, R.sup.8 is a branched
alcohol group.
[0026] In a preferred embodiment, the HALS is a NOR-type hindered
amine light stabilizer wherein the HALS is according to Formula IIa
or IIb, wherein R is connected via an oxygen atom (--OR.sup.8);
R.sup.8 is an optionally substituted, optionally branched alkyl
group having between 2 and 10 carbon atoms, such as between 3 and 5
carbon atoms. It was surprisingly found a polymer composition
comprising a NOR-type HALS has improved heat resistance and
weatherability. For example, the NOR-type HALS has the following
structure:
##STR00003##
[0027] NOR-type HALS is commercially available, for instance,
Tinuvin.RTM. XT 855 FF from BASF.
[0028] In an embodiment, the inorganic acid scavenger is a
hydrotalcite. In a preferred embodiment, this hydrotalcite is of
the chemical family of aluminium-magnesium-carbonate-hydroxide
(hydrate), with the following formula:
Mg.sub.4.3Al.sub.2(OH).sub.12.6CO.sub.3-mH.sub.2O. This compound
has CAS no. 11097-59-9, and is commercially available for instance
as Hycite.RTM. 713 of Clariant.
[0029] In an embodiment, the composition further comprises a
sterically hindered phenolic antioxidant. In a preferred embodiment
this sterically hindered phenolic antioxidant is a polyphenolic
antioxidant. In a preferred embodiment this polyphenolic
antioxidant is
tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), and is
commercially available for instance as Irganox.RTM. 1010 from
BASF.
[0030] In an embodiment, the composition further comprises a
phosphite (secondary) antioxidant. In a preferred embodiment, this
phosphite antioxidant is bis-t-butyl phenyl phosphite; and is
commercially available for instance as Irgafos 168 from BASF.
[0031] In an embodiment, the thioether compound is present in an
amount of between 0.10 and 1.0 wt. % of the total polymer
composition. In a preferred embodiment the thioether compound is
present in an amount of between 0.30 and 0.60 wt. % of the total
polymer composition.
[0032] In an embodiment, the Hindered Amine Light Stabilizer is
present in an amount of between 0.05 and 0.75 wt. % of the total
polymer composition. In a preferred embodiment, the Hindered Amine
Light Stabilizer is present in an amount of between 0.15 and 0.40
wt. % of the total polymer composition.
[0033] In an embodiment, the inorganic acid scavenger compound is
present in an amount of between 0.05 and 0.75 wt. % of the total
polymer composition. In an preferred embodiment, the inorganic acid
scavenger compound is present in an amount of between 0.10 and 0.40
wt. % of the total polymer composition.
[0034] In an embodiment, the composition further comprises short
glass fibre. In a preferred embodiment, the short glass fibre is
present in an amount of between 15 and 50 wt. % of the total
polymer composition, preferably at least 25 wt. %, more preferably
at least 28 wt. %, preferably at most 35 wt. %, more preferably at
most 32 wt. %; such as between 25 and 35 wt. % or between 28 and 32
wt. %.
[0035] In an embodiment, the article according to the invention is
an outdoor article. In a preferred embodiment, the article is a
housing for an antenna for wireless communication.
[0036] Other variations to the disclosed embodiments can be
understood and effected by those skilled in the art in practicing
the claimed invention, from a study of the drawings, the
disclosure, and the appended claims. In the claims, the word
"comprising" does not exclude other elements or steps, and the
indefinite article "a" or "an" does not exclude a plurality. The
scope of the present invention is defined by the appended claims.
One or more of the objects of the invention are achieved by the
appended claims.
EXAMPLES
[0037] The present invention is further elucidated based on the
Examples below which are illustrative only and not considered
limiting to the present invention.
[0038] Methods
[0039] The composition in prepared by compounding in a twin screw
extruder as pellets, then testing sample preparation is done by
single screw extrusion using the prepared pellets.
[0040] Chalking grade is determined according to ISO4892-2, after
1000 hr weathering. The chalking grade is expressed in a number
between 0 and 5, using the following definition: 0=unchanged,
1=very slight change, 2=slight change, 3=moderate change,
4=considerable change, 5=severe change.
[0041] The notched Izod impact strength is determined according to
ISO 180 at 23.degree. C. Retention of the notched Izod impact
strength is determined as the percentage of impact strength
remaining after 1950 h at 150.degree. C.
[0042] Materials
[0043] All (comparative) examples comprise a polypropylene impact
copolymer (PP-I1), being Yungsox 3003 of Formosa (CAS no.
9010-79-1), having a melt index of 0.35 g/10 min (determined
according to ISO 1133:1-2011). This impact copolymer comprises 15.7
wt. % of dispersed phase. The total amount of ethylene-based units
(C2) in the copolymer (TC2) is 8.3 wt. %. The amount of
ethylene-based units (C2) in the dispersed phase (RCC2) is 52.9 wt.
%
[0044] All (comparative) examples comprise a high stiffness impact
copolymer (PP-I2), being Moplen EP5079 of LyondellBasell, with a
melt flow rate (at 230.degree. C., 2.16 kg) of 0.5 g/10 min.
(determined according to ASTM D1238-13). This impact copolymer
comprises 13.5 wt. % of dispersed phase. The total amount of
ethylene-based units (C2) in the copolymer (TC2) is 5.8 wt. %. The
amount of ethylene-based units (C2) in the dispersed phase (RCC2)
is 43.0 wt. %
[0045] All (comparative) examples comprise an ethylene octene
copolymer as a toughening agent (TA), being Fortify C1055D of
SABIC, with a melt flow rate (at 230.degree. C., 2.16 kg) of 2.2
g/10 min (at 190.degree. C., 2.16 kg) or 1.0 g/10 min (determined
according to ASTM D1238-13), a density of 857 kg/m.sup.3 (ASTM
D792-10(2015)) (determined according to ASTM D1238-13).
[0046] All (comparative) examples comprise a maleic anhydride
modified homo polypropylene resin as compatibilizer (CP), being
Bondyram 1010 by Polyram, with a melt flow rate (at 190.degree. C.,
2.16 kg) of 200 g/10 min (determined according to ISO1133:1-2011),
a density of 0.90 g/cm3 (determined according to ISO1183), a
melting point of 160.degree. C. (determined with DSC), and a maleic
anhydride concentration of 1.0% (determined with FTIR).
[0047] All (comparative) examples comprise a color master batch
(CMB) with light grey color.
[0048] All (comparative) examples comprise short glass fiber (SGF)
with CAS No. 65997-17-3 with sizing on surface to improve the
compatibility of the short glass fiber and polypropylene. The short
glass fiber has a diameter of 10 .mu.m and a length of 4 mm. It is
available from Owens Corning (OVC.TM. Reinforcements) under the
name Performax 249A-10C.
[0049] All (comparative) examples comprise a polyphenolic
antioxidant (Phen.AO), being Irganox.RTM. 1010 (pentaerythritol
tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate))
available from BASF.
[0050] All (comparative) examples comprise a phosphite antioxidant
(Phos.AO), being Irgafose.RTM. 168 (bis-t-butyl phenyl phosphite)
available from BASF.
[0051] (Comparative) Examples 1, 5-8 comprise a thiosynergistic
heat stabilizer, being Irganox.RTM. PS 802 FL by BASF (thioether).
It is a dialkyl ester of thiodipropionic acid, with CAS no:
693-36-7.
[0052] (Comparative) Examples 1-4, 7-8 comprise a NOR-type (NOR
HALS) hindered amine light stabilizer Tinuvin.RTM. XT 855 FF from
BASF.
[0053] Comparative Example 5 comprises a high molecular weight N-H
type (NH HALS 1) hindered amine light stabilizer, being
Chimassorb2020 of BASF, with CAS no. 192268-64-7, with a molecular
weight of 2,600-3,4-g/mol, a melting range of 120-150.degree. C., a
volatility (determined with thermogravimetric analysis, in air at
20.degree. C./min) expressed as the temperature at 1% weight loss
of 290.degree. C. and expressed as the temperature at 10% weight
loss of 355.degree. C. The structural formula of this HALS is as
follows.
##STR00004##
[0054] Comparative Example 6 comprises a mixture with its main
component is low molecular weight N-H type HALS (NH HALS 2),
further comprising a UV-absorber, the mixture being V703 by Cytec,
with melting range 51-60.degree. C., a relative density of 1.160
(25.degree. C.) and a UV absorber wavelength range of 270-340
nm.
[0055] Comparative Examples 1-6 comprise an inorganic acid
scavenger (Inorg.AS), being Hycite.RTM. 713 of Clariant, with CAS
number: 11097-59-9 of the chemical family of
aluminium-magnesium-carbonate-hydroxide (hydrate), with a molar
ratio of MgO to Al.sub.2O.sub.3 of between 4 and 5. Comparative
Example 7 comprises an organic acid scavenger (Org.AS), being
calcium stearate.
[0056] All (comparative) examples comprise a high performance
nucleating agent (NA) for polyolefins, being Hyperform HPN-68L of
Milliken. All (comparative) examples comprise a fluoropolymer based
processing additive (PA1), being Fluoro-polymer PPA2300 of Purvan,
with a particle size of 25 mesh, bulk density of 0.72 g/cm.sup.3, a
melting point of 60.degree. C., a volatile percentage (105.degree.
C., 1 h) of 0.12%.
[0057] All (comparative) examples comprise a mold release agent
(MR), being N,N'-ethylene bis stearamide, commercially available as
Kenamide EBS of PMC biogenix or Crodamide ORV of Sichuan SIPO
Chemical or Acrawax C of Lonza, with CAS No. 110-30-5. Typical
properties of this compound are a flash point (COC) of 296.degree.
C. and a fire point of 315.degree. C.
[0058] All (comparative) examples comprise as processing additive
(PA2) an ultra-high molecular weight siloxane polymer, dispersed in
polypropylene homopolymer, being MB50-001 Masterbatch of Dow
Corning, with a siloxane content of 50%, further comprising an
organic resin polypropylene. This compound improves the surface
quality, such as smoothness and gloss.
[0059] The composition of all (comparative) examples is indicated
in Table 1 below in wt. %.
TABLE-US-00001 Ex1 CE2 CE3 CE4 CE5 CE6 CE7 CE8 PP-I1 25.80 25.80
25.80 25.80 25.80 25.80 25.80 25.90 PP-I2 25.80 26.00 25.75 25.50
25.80 25.80 25.80 25.90 TA 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00
CP 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 CMB 3.00 3.00 3.00 3.00
3.00 3.00 3.00 3.00 SGF 32.00 32.00 32.00 32.00 32.00 32.00 32.00
32.00 Phen. AO 0.30 0.50 0.75 1.00 0.30 0.30 0.30 0.30 Phos. AO
0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 Thioether 0.40 n.p. n.p.
n.p. 0.40 0.40 0.40 0.40 N-OR HALS 0.30 0.30 0.30 0.30 n.p. n.p.
0.30 0.30 N-H HALS1 n.p. n.p. n.p. n.p. 0.30 n.p. n.p. n.p.
NH-HALS2 n.p. n.p. n.p. n.p. n.p. 0.30 n.p. n.p. Inorg. AS 0.20
0.20 0.20 0.20 0.20 0.20 n.p. n.p. Org. AS n.p. n.p. n.p. n.p. n.p.
n.p. 0.20 n.p. NA 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 PA1 0.20
0.20 0.20 0.20 0.20 0.20 0.20 0.20 MR 0.55 0.55 0.55 0.55 0.55 0.55
0.55 0.55 PA2 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 n.p = not
present
[0060] The retention of notched Izod impact strength, as well as
the chalking grade are indicated below for all (comparative)
examples.
TABLE-US-00002 Ex1 CE2 CE3 CE4 CE5 CE6 CE7 CE8 Retention (%) 80.8
51.5 52.6 64.2 78.5 75.7 72.5 86.9 Chalking 0 0 0 0 3 3 3 2
grade
[0061] By comparing Ex1 with CE2, CE3 and CE4, it becomes clear
that the addition of a thioether compound according to Formula I
leads to improved retention.
[0062] By comparing Ex1 with CE5 and CE6, it becomes clear that the
presence of a NOR type HALS leads to improved retention and
chalking grade compared to an NH type HALS.
[0063] By comparing Ex1 with CE7 and CE8, it becomes clear that the
presence of an inorganic acid scavenger leads to an improved
retention and chalking grade compared to an organic or no acid
scavenger.
* * * * *